Spectroscopic study of the highly homogeneous polyaniline film formation on gold support

• Experimental evidence of highly homogeneous polyaniline film formation.
• Spectroscopic monitoring of the self-assembly and film formation.
• Unique series of experiments consisting in the immersion of gold supports in the reaction mixture.
• The mechanism of the film formation and surface interaction of aniline oligomers with gold support.

The oxidation of aniline with ammonium peroxydisulfate in the aqueous solution of acetic acid has two subsequent phases: the oxidation of the neutral aniline molecules at low acidity, which was followed by the oxidation of the anilinium cations after the acidity became higher. The final polyaniline film deposited on immersed surfaces is usually contaminated with semi-crystalline oligomers which precipitated during induction period from the reaction medium. To obtain a homogeneous film, which is important in the fabrication of many molecular electronic devices, we have studied the course of aniline oxidation in a view of new experimental evidence. In the unique series of experiments, the silicon or gold supports have been immersed in the reaction mixture at crucial stages of oxidation reaction, and the deposits at the end of the reaction were analyzed. The growth of a highly homogenous film on the gold-coated glass substrate immersed in the reaction mixture at the end of the polymerization period has been observed. The molecular structure of the products was monitored with UV–visible, infrared, and Raman spectroscopies. The possible mechanism of the film formation and the molecular mechanism of the surface interaction of chemisorbed aniline oligomers with gold support are proposed.

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